EP0336622B1 - Kohlenwasserstoff-Dehydrierungsreakionen - Google Patents

Kohlenwasserstoff-Dehydrierungsreakionen Download PDF

Info

Publication number
EP0336622B1
EP0336622B1 EP89302985A EP89302985A EP0336622B1 EP 0336622 B1 EP0336622 B1 EP 0336622B1 EP 89302985 A EP89302985 A EP 89302985A EP 89302985 A EP89302985 A EP 89302985A EP 0336622 B1 EP0336622 B1 EP 0336622B1
Authority
EP
European Patent Office
Prior art keywords
stage
catalyst
process according
dehydrogenation
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP89302985A
Other languages
English (en)
French (fr)
Other versions
EP0336622A2 (de
EP0336622A3 (en
Inventor
Andrew Holt
Paul Christopher James Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Chemicals Ltd
BP PLC
Original Assignee
BP Chemicals Ltd
BP PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP Chemicals Ltd, BP PLC filed Critical BP Chemicals Ltd
Publication of EP0336622A2 publication Critical patent/EP0336622A2/de
Publication of EP0336622A3 publication Critical patent/EP0336622A3/en
Application granted granted Critical
Publication of EP0336622B1 publication Critical patent/EP0336622B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides

Definitions

  • the present invention relates to a method of improving hydrocarbon dehydrogenation reactions e.g. dehydrogenation of ethylbenzene to styrene.
  • the catalyst described in the above patent contains a Group VIII metal, a Group IVA metal (both present at up to 5 wt%) and a Group IA/IIA metal (up to 10 wt%) impregnated or co-precipitated on a highly porous inorganic support.
  • a support such as alumina is detrimental to the process because it causes the cracking of a large amount of ethylbenzene and styrene to benzene and toluene by-products, which greatly reduces the selectivity of the process.
  • the present invention is a process for the dehydrogenation of hydrocarbons, said process comprising at least three stages which consist essentially of
  • the hydrocarbons that may be catalytically dehydrogenated by this process include C2-C20 linear, branched or cyclic alkanes, alkenes, polyenes or alkyl aromatics.
  • alkanes can be dehydrogenated to olefins, cycloalkanes to cyclic olefins, olefins to diolefins and alkyl aromatics to vinyl aromatics.
  • the process of the present invention is particularly suited to dehydrogenation reactions using a catalyst comprising iron oxide, preferably in the presence of steam.
  • the iron oxide catalyst is preferably Fe3O4. This catalyst species can be derived by the reduction of commercially available Fe2O3 catalyst.
  • the reduction of Fe2O3 can be carried out prior to use in the dehydrogenation step or 'in situ', for instance by conditioning over a duration in the dehydrogenation reactor where significant quantities of hydrogen are readily available for this purpose.
  • a typical example of such a reaction is the dehydrogenation of alkylaromatic hydrocarbons to vinyl aromatic hydrocarbons, especially the dehydrogenation of ethylbenzene to styrene.
  • GB-A-1176916 (Badger) describes this type of process.
  • the dehydrogenation of ethyl benzene to styrene is an endothermic reaction. It is therefore, conventional to supply this reaction with the necessary heat e.g. by mixing quantities of superheated steam with the hydrocarbon.
  • the steam serves to maintain the selected dehydrogenation temperature, to prevent coke deposition on the catalyst used and to reduce the partial pressure of the reactants.
  • the dehydrogenation reaction is suitably carried out at a temperature from 500-700°C, preferably from 600-650°C,.
  • the dehydrogenation reaction is suitably carried out at a pressure ranging from 0.1 to 10 atmospheres, preferably from 0.1 - 1 atmosphere.
  • the feed rate of steam to hydrocarbon on a weight basis is suitably from 1:1 to 10:1, preferably from 1:1 to 5:1.
  • the liquid hourly space velocity (LHSV) based on the feed hydrocarbon may vary from 0.1 - 10 hr ⁇ 1, preferably from 0.1 - 2 hr ⁇ 1.
  • the gaseous mixture from the first stage is then passed onto a second stage.
  • the gaseous mixture is brought into contact with a hydrogen removal catalyst in the presence of oxygen or a gas containing molecular oxygen.
  • the gas containing molecular oxygen is suitably air.
  • the amount of oxygen or gas containing molecular oxygen introduced into this second stage may vary from 0.1:1 to 1:1 moles of oxygen per mole of hydrogen contained in the gaseous mixture emerging from the first stage, preferably from 0.4 to 0.6 moles of oxygen per mole of hydrogen. Within these ranges the amount of oxygen or gas containing molecular oxygen used should be such that all the oxygen fed is consumed in the hydrogen removal stage and no oxygen emerges from or is contained in the feed to the third stage.
  • the amount of hydrogen in the gaseous mixture entering the second stage can be monitored by conventional sampling techniques.
  • the oxygen is suitably introduced into the second stage along with the gaseous mixture emerging from the first stage.
  • the oxygen or the gas containing molecular oxygen is preferably introduced immediately prior to contact with a bed of the hydrogen removal catalyst.
  • the hydrogen removal catalyst in the second stage comprises an oxide of one or more Group VIII metals selected from palladium, platinum, rhodium and ruthenium supported on a tin oxide support.
  • the metal oxide catalyst for this stage can be preformed e.g. by depositing the oxide(s) or a compound capable of giving rise to the respective oxide(s) on the tin oxide support followed by calcination in air at elevated temperature.
  • the compound capable of giving rise to the oxide(s) can be deposited on the tin oxide support and the respective oxide(s) generated in situ in the hydrogen removal reactor where the catalyst is subjected to elevated temperatures in the presence of air.
  • Examples of such compounds capable of giving rise to the metal oxides include metal salts and their complexes such as the chlorides, the nitrates, the sulphates and the amine chlorides of these metals.
  • Palladium and platinum compounds are most preferred.
  • the palladium compound is suitably palladium nitrate.
  • the compound used is suitably chloroplatinic acid. Whichever compound(s) is/are used, they are deposited on a tin oxide support and then calcined at elevated temperature to form the respective metal oxide(s) on the tin oxide support.
  • the Group VIII metal oxide is preferably that of palladium and/or platinum.
  • the amount of Group VIII metal(s) in the hydrogen removal catalyst composition is suitably 0.01 to 20% by weight, preferably from 0.1 to 10% by weight based on the total catalyst inclusive of the support.
  • the amount of tin oxide support in the catalyst is greater than 5% w/w, suitably greater than 10% w/w, preferably at least 15% w/w based on the total weight of the catalyst and support.
  • the palladium tin oxide hydrogen removal catalyst may also be mixed with diluents which are inert under the reaction conditions such as MgO, CaO etc which reduce the total content of the Group VIII metal in the catalyst to a desired concentration.
  • diluents which are inert under the reaction conditions such as MgO, CaO etc which reduce the total content of the Group VIII metal in the catalyst to a desired concentration.
  • These inert diluents may be present at concentrations of up to 95 wt%.
  • liquid hourly space velocity (LHSV) based on the hydrocarbon content of the gaseous mixture for this stage is the same as for stage (a) above.
  • the hydrogen removal catalyst for the second stage is suitably prepared by intimately mixing the Group VIII metal compound, e.g. the palladium nitrate and chloroplatinic acid with the tin oxide to form a homogeneous mixture which is then formed into a dough by kneading with a dilute acid e.g. nitric acid.
  • the dough is then divided into smaller lumps and dried in an oven at elevated temperature in air e.g. at about 100°C-120°C for up to 24 hours.
  • the dried catalyst is then calcined at elevated temperature, e.g. up to 350°C in air for a duration until the metal compounds are transformed into the respective oxides.
  • the calcined sample is then crushed, sieved and then pelletised e.g. with graphite or carbon.
  • the presence of oxygen enables the hydrogen in the gaseous reaction mixture from the first stage to be oxidised. This is an exothermic reaction and enables the temperature of the second stage catalyst to be maintained at the desired range.
  • the second stage hydrogen removal catalyst comprising a Group VIII metal oxide supported on tin oxide is maintained at a temperature which is suitably from 300 to 700°C, preferably 500 to 700°C at the time of contact with the gaseous reaction mixture from the first stage.
  • the gaseous mixture of hydrocarbons emerging from this second stage and substantially free from any oxygen or gas containing molecular oxygen is then fed into the third stage where the mixture is subjected to a further dehydrogenation.
  • the dehydrogenation conditions in this third stage are substantially similar to those employed in the first stage. In order to maximise the yield of desired dehydrogenated product, this third stage is essential.
  • the resultant products from this third stage can be purified by conventional processes to recover the final dehydrogenated product.
  • the dehydrogenation process of the present invention has at least three stages at least two of which are dehydrogenation stages, but may be a multi-stage process suitably having in all 3-5 stages.
  • the process of the present invention can be operated batchwise or continuously.
  • dehydrogenated products e.g. such as the vinyl aromatic hydrocarbon styrene are starting materials used in a variety of resins, plasticisers, elastomers, synthetic rubbers and the like.
  • the mull of tin oxide was mixed for 15 minutes to homogenise in a Z blade mixer.
  • the mixed dough was then dried at 105°C for 10 hrs and finally calcined in air to 350°C.
  • the lumps of oxide catalyst were crushed to 240 microns, mixed with 1 % wt graphite and the powder pelleted into 4.8 x 4.8 mm cylinders.
  • Figure 1 shows the experimental set-up used during the examples.
  • Reactor 1 (12" long and 1" I.D.) was charged with 100 grams (80 mls) of a commercial iron oxide catalyst (Girdler G64I), which was previously conditioned by operating in a styrene reactor for 3 days. The remaining space at the top of the reactor was filled with inert diluent in the form of cylindrical ceramic beads (4 mm x 4 mm), which acted as a preheating zone.
  • a commercial iron oxide catalyst (Girdler G64I)
  • Reactor 2 (18" long and 1" I.D.) incorporates the second and third stage reactors as Section 1 and Section 2 respectively.
  • Section 1 was charged with 150 gms (85 mls) of the platinum oxide -palladium oxide-tin oxide catalyst prepared as in Section A above. The space at the top of Section 1 was filled with inert ceramic beads.
  • Section 2 of this reactor was also charged with 100 grams (80 mls) of Girdler G64I iron oxide catalyst.
  • Nitrogen was fed to the two Reactors 1 and 2 at 6 l/hr while the two Reactors were brought up to 500°C at atmospheric pressure. Water was then fed to the two Reactors at 70 g/hr. The temperature in Reactor 1 was then increased to 570°C. The temperature in Section 1 of Reactor 2 (containing the Pt, Pd/SnO2 catalyst) was increased to 550°C, and the temperature in Section 2 (containing the iron oxide catalyst) was increased to 600°C. At this stage the nitrogen stream was switched off. Ethylbenzene of 99.6% purity was then fed to Reactor 1 at 40 g/hr and the reactor temperatures allowed to stabilise for 2 hours.
  • Reactor 1 was at 570°C
  • Section 1 of Reactor 2 was at 550°C
  • Section 2 of Reactor 2 was at 600°C.
  • Air was then fed into Section 1 of Reactor 2 at a rate of 7 l/hr, and the system allowed to stabilise as previously for a further 2 hours.
  • the product from Reactors 1 and 2 were sampled. The results are shown in Table 1.
  • Example 2 This was carried out after a further 3 hours on stream.
  • the conditions used were the same as Example 1, except no air was fed to the system.
  • Tin oxide powder was calcined in flowing air to 350°C/4 hours. 252.93g of the powder was then slurried with 100 cm3 of 10%v/v HNO3 (aq) and the mixture stirred for 10 minutes. Tetramine palladium (11) nitrate (56.65g of a 4.51 %wt Pd solution) was added to the tin oxide slurry and stirred for 30 minutes. The slurry was then rotary evaporated to dryness and tray dried overnight at 105°C.
  • the powder was then calcined in flowing air according to the following profile: 50 - 150°C, 100°C/hr, hold 2 hours 150 - 350°C, 100°C/hr, hold 2 hours 350 - 600°C, 100°C/hr, hold 4 hours
  • the powder was then mixed with 1% wt graphite and pelleted.
  • Example 1 The reactors were set up as in Example 1 except that section 1 of reactor 2 was charged with 100 g (56 ml) of the palladium oxide-tin oxide catalyst prepared as in Section A above.
  • the experimental conditions and product analyses are shown in Table 1.
  • Example 3 The reactors were set up as in Example 3 above except that the palladium oxide-tin oxide catalyst had been removed from Section 1 of reactor 2 and replaced with inert ceramic beads.
  • the reactors were commissioned as in Example 1 above, except that there was no air flow to the reactors.
  • the temperature of the reactors were the same as for Example 3 above.
  • Tin oxide powder was calcined in flowing air to 350°C/4 hours. 250.48g of the powder was then slurried with 100 cm3 of 10% v/v HNO3 (aq) and the mixture stirred for 10 minutes. Tetramine palladium (11) nitrate (27.94g of a 4.51%wt Pd solution) was added to the tin oxide slurry and stirred for 30 minutes. The slurry was then rotary evaporated to dryness and tray dried overnight at 105°C.
  • the powder was then calcined in flowing air according to the following profile: 50 - 150°C, 100°C/hr, hold 2 hours 150 - 350°C, 100°C/hr, hold 2 hours 350 - 600°C, 100°C/hr, hold 4 hours
  • the powder was then mixed with 1%wt graphite and pelleted.
  • Example 1 The reactors were set up as in Example 1 except that Section 1 of reactor 2 was charged with 45 gms (25 mls) of the palladium oxide-tin oxide catalyst prepared as in Section A above.
  • the experimental conditions and product analyses are shown in Table 1.
  • Example 4 After completion of Example 4 the temperature of Section 1 of reactor 2 was reduced to 550°C with all other conditions remaining constant. The product from reactors 1 and 2 were sampled after approximately a 3 hour period. The benefit of the increased styrene yield is evident when compared against Comparative Test 4.
  • Example 1 The reactors were set up as in Example 1 except that Section 1 of reactor 2 was charged with 100 gms (80 mls) of the palladium oxide-tin oxide-magnesium oxide catalyst prepared as in Section A above.
  • the experimental conditions and product analyses are shown in Table 1. The benefit of the increased styrene yield is evident when compared against Comparative Test 4.
  • Example 1 The reactors were set up as in Example 1 except that Section 1 of reactor 2 was charged with 88 gms (77 mls) of the palladium oxide-tin oxide-magnesium oxide catalyst prepared as in Section A above.
  • the experimental conditions and product analyses are shown in Table 1. The benefit of the increased styrene yield is evident when compared against Comparative Test 4.
  • the tin oxide supported catalyst used was the same as that used in Example 4.
  • Example 1 The reactors were set up as in Example 1 except that Section 1 of reactor 2 was charged with 100 gms (58 mls) of the palladium oxide-tin oxide catalyst prepared as in Section A above. In addition, there was no iron oxide dehydrogenation catalyst present in Section 2 of reactor 2.
  • Table 1 The experimental conditions and product analyses are shown in Table 1.
  • This catalyst containing 0.5% Pd on gamma-alumina, was purchased ready made from United Catalysts Inc. Its surface area was 206 m2/g, which is within the range of surface areas described in US Patent 4435607.
  • the reactors were set up as in Example 8 above except that 40 gms (50 mls) of the palladium oxide-alumina catalyst was charged to Section 1 of reactor 2 in place of the palladium oxide-tin oxide catalyst.
  • the experimental conditions and product analyses are shown in Table 1. The results clearly show the much higher formation of benzene and toluene by-products when using the alumina-supported catalyst compared with the tin oxide supported catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (13)

1. Verfahren zur Dehydrierung von Kohlenwasserstoffen, wobei das Verfahren wenigstens drei Schritte umfaßt, bestehend im wesentlichen aus
(a) einem ersten Schritt, worin der Kohlenwasserstoff bei erhöhter Temperatur katalytisch dehydriert wird in eine gasförmige Mischung, die das dehydrierte Produkt und Wasserstoff enthält,
(b) einem zweiten Schritt, worin die gasförmige Mischung aus dem ersten Schritt bei erhöhter Temperatur mit Sauerstoff oder einem molekularen Sauerstoff enthaltenden Gas umgesetzt wird, in Anwesenheit eines Wasserstoffentfernungskatalysators, der ein Oxid einer oder mehrerer Metalle der Gruppe VIII, ausgewählt unter Palladium, Platin, Rhodium und Ruthenium, das an einem Zinnoxid gestützt ist, umfaßt, wobei der Träger anwesend ist in einer Menge größer als 5% Gew./Gew. des Gesamtgewichts des Katalysators und Trägers, und
(c) einem dritten Schritt, worin die aus dem zweiten Schritt entstandene, gasförmige KohlenwasserstoffMischung unter denselben Bedingungen wie in Schritt (a) oben dehydriert wird.
2. Verfahren nach Anspruch 1, worin der Kohlenwasserstoff ein C₂-C₂₀ lineares, verzweigtes oder zyklisches Alkan, Alken, Polyen oder Alkyl-aromatische Substanz ist.
3. Verfahren nach Anspruch 1 oder 2, worin der Kohlenwasserstoff ein zu Styrol dehydriertes Ethylbenzol ist.
4. Verfahren nach einem der vorhergehenden Ansprüche, worin der Dehydrierungskatalysator für Schritt (a) Eisenoxid umfaßt.
5. Verfahren nach einem der vorhergehenden Ansprüche, worin der Dehydrierungskatalysator für Schritt (a) ein von Fe₂O₃ in situ während der Dehydrierungsrekation abgeleitetes Fe₃O₄ ist.
6. Verfahren nach einem der vorhergehenden Ansprüche, worin der Dehydrierungssschritt (a) in Anwesenheit von Dampf durchgeführt wird.
7. Verfahren nach einem der vorhergehenden Ansprüche, worin der Dehydrierungsschritt (a) bei einer Temperatur von 500-700°C und einem Druck von 0,1 bis 10 Atmosphären durchgeführt wird.
8. Verfahren nach einem der vorhergehenden Ansprüche 4 bis 7, worin der LHSV für Kohlenwasserstoff-Zuführung, bezogen auf den Eisenoxid-Katalysator 0,1-10hr⁻¹ beträgt.
9. Verfahren nach einem der vorhergehenden Ansprüche, worin die aus Schritt (a) entstandene gasförmige Mischung mit einem Wasserstoffentfernungskatalysator, der eines oder mehrere der Metalloxide der Gruppe VIII, die an Zinnoxid gestützt werden, umfaßtf in Schritt (b) in Kontakt gebracht wird, wobei das Metalloxid in situ aus einer Verbindung erzeugt wird, die Metalloxid unter den Reaktionsbedingungen entstehen läßt.
10. Verfahren nach einem der vorhergehenden Ansprüche, worin der Wasserstoffentfernungskatalysator ein unter den Reaktionsbedingungen inertes Verdünnungsmittel enthält.
11. Verfahren nach einem der vorhergehenden Ansprüche, worin die Menge an Sauerstoff oder molekularen Sauerstoff enthaltendes Gas, die in Schritt (b) eingeführt wird, von 0,1:1 bis 1:1 Mol Sauerstoff pro Mol Wasserstoff, der in der aus Schritt (a) entstandenen, gasförmigen Mischung, enthalten ist, variiert.
12. Verfahren nach einem der vorhergehenden Ansprüche, worin der Wasserstoffentfernungskatalysator bei einer Temperatur von 300-700°C während Schritt (b) gehalten wird.
13. Verfahren nach einem der vorhergehenden Ansprüche, worin die aus Schritt (b) entstandene gasförmige Mischung im wesentlichen von Sauerstoff oder molekularen Sauerstoff enthaltenden Gasen befreit wird vor der Dehydrierung in schritt (c).
EP89302985A 1988-03-31 1989-03-23 Kohlenwasserstoff-Dehydrierungsreakionen Expired EP0336622B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888807732A GB8807732D0 (en) 1988-03-31 1988-03-31 Hydrocarbon dehydrogenation reactions
GB8807732 1988-03-31

Publications (3)

Publication Number Publication Date
EP0336622A2 EP0336622A2 (de) 1989-10-11
EP0336622A3 EP0336622A3 (en) 1989-11-23
EP0336622B1 true EP0336622B1 (de) 1992-05-06

Family

ID=10634457

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89302985A Expired EP0336622B1 (de) 1988-03-31 1989-03-23 Kohlenwasserstoff-Dehydrierungsreakionen

Country Status (6)

Country Link
US (1) US5001291A (de)
EP (1) EP0336622B1 (de)
CA (1) CA1308744C (de)
DE (1) DE68901414D1 (de)
ES (1) ES2030971T3 (de)
GB (1) GB8807732D0 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5563314A (en) * 1993-08-27 1996-10-08 Agaskar; Pradyot A. Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen
DK171414B1 (da) * 1993-11-30 1996-10-21 Topsoe Haldor As Fremgangsmåde til carbonhydrid dehydrogenering
NO300117B1 (no) * 1994-12-22 1997-04-14 Norske Stats Oljeselskap Reaktor for dehydrogenering av hydrokarboner med selektiv oksidasjon av hydrogen
US5994606A (en) * 1995-03-08 1999-11-30 Mitsubishi Chemical Corporation Method for dehydrogenation of hydrocarbon
EP0730906B1 (de) * 1995-03-08 1999-08-11 Mitsubishi Chemical Corporation Verfahren für die selektive Oxidation von Wasserstoff und für die Dehydrierung von Kohlenwasserstoffen
DE19601750A1 (de) * 1996-01-19 1997-07-24 Basf Ag Verfahren zur Oxidation und Oxidehydrierung von Kohlenwasserstoffen in der Wirbelschicht
IT1292390B1 (it) * 1997-06-20 1999-02-08 Snam Progetti Sistema catalitico e procedimento per deidrogenare l'etilbenzene a stirene
AU8130898A (en) * 1997-07-17 1999-02-10 Mitsubishi Chemical Corporation Process for producing styrene
US20070078053A1 (en) * 2005-09-30 2007-04-05 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Catalyst for decomposition of nitrogen oxides
DE102006035718A1 (de) 2006-07-28 2008-01-31 Basf Ag Verfahren zum Langzeitbetrieb einer kontinuierlich betriebenen heterogen katalysierten partiellen Dehydrierung eines zu dehydrierenden Kohlenwasserstoffs
US20120078024A1 (en) * 2010-09-24 2012-03-29 Fina Technology Inc. Removal of Hydrogen From Dehydrogenation Processes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1405405A (en) * 1971-06-25 1975-09-10 Johnson Matthey Co Ltd Platinum group metal catalysts
US4435607A (en) * 1981-04-28 1984-03-06 Uop Inc. Dehydrogenation of dehydrogenatable hydrocarbons
ATE28171T1 (de) * 1982-03-12 1987-07-15 Cjb Developments Ltd Verfahren zur abscheidung von wasserstoff aus gasen.
US4565898A (en) * 1985-03-06 1986-01-21 Uop Inc. Dehydrogenation of dehydrogenatable hydrocarbons
US4717779A (en) * 1985-09-11 1988-01-05 Uop Inc. Dehydrogenation of dehydrogenatable hydrocarbons
US4652687A (en) * 1986-07-07 1987-03-24 Uop Inc. Process for the dehydrogenation of dehydrogenatable hydrocarbons
US4691071A (en) * 1986-12-11 1987-09-01 Uop Inc. Dehydrogenation of dehydrogenatable hydrocarbons

Also Published As

Publication number Publication date
ES2030971T3 (es) 1992-11-16
EP0336622A2 (de) 1989-10-11
EP0336622A3 (en) 1989-11-23
GB8807732D0 (en) 1988-05-05
DE68901414D1 (de) 1992-06-11
US5001291A (en) 1991-03-19
CA1308744C (en) 1992-10-13

Similar Documents

Publication Publication Date Title
CA1292248C (en) Steam dehydrogenation and oxidative reheat process using only one catalyst system
KR100333002B1 (ko) 촉매의개량
US3912787A (en) Selective partial hydrogenation of aromatics
US4486547A (en) Indium-containing dehydrogenation catalyst
US4886928A (en) Hydrocarbon dehydrogenation process
US4780449A (en) Catalyst for the conversion of methane
EP0230769B1 (de) Verfahren zur Oxidierung von Methan in Gegenwart von heterogenen Katalysatoren
EP0212850A1 (de) Dehydrierverfahren und Katalysator
EP0082641B1 (de) Katalysatoren für die Herstellung von Alkoholen aus Olefinen und Synthesegas und solche Katalysatoren verwendendes Verfahren
EP0227750A4 (de) Verfahren und katalysator zur umwandlung von methan.
EP0560437A1 (de) Katalysatorzusammensetzung zur Dehydrierung von C2-C5-Paraffinen
EP0336622B1 (de) Kohlenwasserstoff-Dehydrierungsreakionen
US4551574A (en) Indium-containing dehydrogenation catalyst
JP4706945B2 (ja) 優れたアクセシビリティーを有する、第８、９または１０族の元素を含む触媒、およびパラフィン脱水素方法におけるその使用
US4177219A (en) Process for selective ethyl scission of ethylaromatics to methylaromatics
US4737595A (en) Hydrocarbon dehydrogenation
EP0370054B1 (de) Katalysator und selektives dehydrierungsverfahren
CA1212374A (en) Dehydrogenation catalyst composition
US5093540A (en) Process for selectively converting linear paraffins to linear alpha olefins
EP0183861B1 (de) Indium enthaltender Dehydrierungskatalysator
JPH05310613A (ja) モノアルケニルベンゼン類の製造方法
US3862255A (en) Oxidative dehydrogenation processes
US4438021A (en) Catalyst for dehydrocoupling of toluene or xylene
US3666824A (en) Hydroealkylation process and catalyst
CN114733521B (zh) 一种双晶型载体的烷烃非氧化脱氢催化剂

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE ES FR GB IT NL

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19891023

17Q First examination report despatched

Effective date: 19910711

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT NL

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 68901414

Country of ref document: DE

Date of ref document: 19920611

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2030971

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20080326

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080327

Year of fee payment: 20

Ref country code: NL

Payment date: 20080324

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080317

Year of fee payment: 20

Ref country code: DE

Payment date: 20080430

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080329

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20090322

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090323

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 20090323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090324